CN1259152A - Polymers with thiol terminal function - Google Patents
Polymers with thiol terminal function Download PDFInfo
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- CN1259152A CN1259152A CN98805803A CN98805803A CN1259152A CN 1259152 A CN1259152 A CN 1259152A CN 98805803 A CN98805803 A CN 98805803A CN 98805803 A CN98805803 A CN 98805803A CN 1259152 A CN1259152 A CN 1259152A
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K8/00—Cosmetics or similar toiletry preparations
- A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q5/00—Preparations for care of the hair
- A61Q5/04—Preparations for permanent waving or straightening the hair
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/002—Dendritic macromolecules
- C08G83/005—Hyperbranched macromolecules
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
- C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
- C09K15/28—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing nitrogen, oxygen and sulfur
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/52—Stabilizers
- A61K2800/522—Antioxidants; Radical scavengers
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/54—Polymers characterized by specific structures/properties
Abstract
The invention concerns novel polymers selected among hyperbranched polymers and dendrimers comprising functional groups of formula (I) in which: Y represents the oxygen atom or a NH group; A represents a linear, branched or cyclic C1-C12 di-yl alkane group, saturated or unsaturated; this di-yl alkane group can optionally be interrupted by one or several heteroatoms, such as O or N; this di-yl alkane group can optionally be substituted by a function: amino: -NH2, optionally in the form of a mineral or organic salt, acylamino: -NH-COR, in which R represents a linear, branched or cyclic C1-C10 alkyl group, saturated or unsaturated, carboxylic acid, C1-C10 ester; X represents a nucleophile group. The invention also concerns a method for preparing them and the use of said dendrimers and/or hyperbranched polymers as antioxidants.
Description
The present invention relates to the novel highly branched dendrimers (dendrimer) and the polymkeric substance that contain thiol functional group, relate to their preparation method and relate to these highly branched dendrimers and/or polymkeric substance purposes as antioxidant.
Many highly-branched polymers and dendrimers early existing people be described.For example referring to people such as D.A.Tomalia, Angew.Chem.Int.Engl.29 (1990) 138-175; N.Ardoin and D.Astruc, Bull.Soc.Chim.Fr (1995) 132,875-909; B.I.Voit, Acta polymer, 46,87-99 (1995).
The possibility for preparing the dendrimers that contains the thiol end group is imagined by some author, for example D.A.Tomalia is in US-4 587 329 and EP-A-234 408, but its preparation method never carries out effectively, does not also mention in the prior art or the surprising performance (according to applicant's explanation) of these molecules of pointing out.
Also have, the method that preparation contains the highly-branched polymers of thiol functional group and dendrimers is novel and has many advantages that good synthesis yield is wherein arranged, and is purchased the easiness of the use and the enforcement of starting raw material.
Highly-branched polymers is the general molecular structure that has branched structure in the core periphery.Its structure generally lacks symmetry: monomer that exists in the highly-branched polymers structure or elementary cell can have various character and their right and wrong are equally distributed.Branch in the polymkeric substance can have various character and length.Elementary cell or monomeric number can be according to different branching and difference.When keeping asymmetry, highly-branched polymers can have: in the peripheral extremely structure of branching of core; The continuous generation (generations) of branching or layer; The layer of end chain.
Highly-branched polymers generally obtains from the polycondensation of one or more monomer A Bx, and A and B are reactive activity groups together, and x is the integer more than or equal to 2, but other preparation method also can consider.Highly-branched polymers can be characterized by their polymerization degree DP=1-b, b be among the B not with the percentage ratio of the non-terminal functional groups of group A reaction.Because condensation reaction is asystematic, synthetic opposite with dendrimers, the polymerization degree is lower than 100%.By known synthetic method, DP usually is between 15-90%.End group T can obtain specific functional group at the end of the chain with the highly-branched polymers reaction.
This polymkeric substance especially is described in B.I.Voit, Acta polymer, 46,87-99 (1995); EP-682 059, WO-96/14346, WO-96/14345, WO-96/12754.
Several highly-branched polymers can link together by means of the keyed jointing mode of covalent linkage or another type by their end group.So-called " bridge joint " polymkeric substance belongs to the definition category of highly-branched polymers of the present invention.
Dendrimers is highly-branched polymers and oligopolymer, is known equally; They have the chemical structure of strict difinition and it is said " perfectly " highly-branched polymers.In general, dendrimers comprises core, ascertain the number by branch, or trunk (spindle) and end group generation (generations) of constituting.The trunk in each generation is made up of structural unit, is identical and these unit can be identical or different for the trunk in different generations for these unit for the trunk in generation.The trunk in each generation radially stretches out from core in geometric growth (geometrical progression) mode.The end group of the dendrimers in N generation is the terminal functional groups of N generation or that monobasic trunk of end.This polymkeric substance especially is described in D.A.Tomalia, A.M.Naylor and W.A.Goddard III, Angewandte Chemie, Int.Ed.Engl.29,138-175 (1990); C.J.Hawker and J.M.J.Frechet, J.Am.Chem.Soc., 112,7638 (1990); B.I.Voit, Acta polymer, 46,87-99 (1995); N.Ardoin and D.Astruc.Bull.Soc.Chim.Fr.132,875-909 (1995).
Specifically dendrimers also can be defined by following formula (DI): C[A
1B
1(A
2B
2(... (A
N-1B
N-1(A
nB
n(T) r
n) r
N-1) r
N-2...) r
2) r
1] s (DI)
Wherein
-C represents core, through group A
1Functional group by number s is connected to s trunk A
1B
1
-s is more than or equal to 1 but is less than or equal to the integer of functional group's number among the C;
-for each trunk (A
iB
i) (i=1,2...n), group B
iBe connected in trunk (A
I+1B
I+1) r
iIndividual group A
I+1
-each group A
i(i 〉=2) are connected in trunk (A
I-1B
I-1) separate base B
I-1
-r
i(i=1 2...n-1) is illustrated in and belongs to trunk (A
iB
i) group B
iIn the number of functional group, r
iIt is integer more than or equal to 2;
(i=1 2...n) is integer to-index i, represents the generation of each trunk.
-Di n is for A
nB
nTrunk be connected in number r with chemical mode
nEnd group T, r
nIt is integer more than or equal to 0.
Dendrimers defined above comprises the molecule that contains symmetrical branching; It also comprises the molecule that contains asymmetric branching, and for example trunk is the dendrimers of Methionin group, and wherein generation trunk occurs on the amine a and e of Methionin in the branching on last generation, and then causes for different branching different trunk length being arranged.
The compactness star polymer, star divergence form polymkeric substance and clavate dendrimers all are included in the definition of this dendrimers.The molecule that is called tree sample branch and cascade shape also drops in the range of definition of dendrimers of the present invention.
Several dendrimers can link together by means of the keyed jointing mode of covalent linkage or another type by their end group, in order that be called the material of " bridge joint dendrimers " or " dendrimers aggregate ".This type of material is included in the dendrimers definition of the present invention.
Dendrimers can be one group (set) same form for molecule, and these are so-called monodispersity groups; They can also be called the polymolecularity group for the form of the group in different generations.The dendrimers that comprises monodispersity group and polymolecularity group according to the definition of dendrimers of the present invention.
The objective of the invention is to be selected from the new polymers of highly-branched polymers and dendrimers, it is characterized in that they contain functional group corresponding to general formula (I):
Wherein: Y represents Sauerstoffatom or NH group, preferred Y=O;
A represents linearity, branching or ring-type, saturated or unsaturated C
1-C
12Alkane 2 basis; This alkane 2 basis can insert one or more heteroatomss in arbitrariness ground, as O or N;
This alkane 2 basis can be replaced by a following functional group to arbitrariness:
-amino :-NH
2, be to arbitrariness form inorganic or organic acid salt,
-amido :-NH-COR, wherein R represents linearity, branching or ring-type, saturated or unsaturated C
1-C
10Alkyl,
-carboxylic acid,
-C
1-C
10Ester;
X represents nucleophilic group, and is preferred: Sauerstoffatom or group-NR '-and, wherein R ' is selected from hydrogen atom; Linearity or branching, saturated or unsaturated C
1-C
6Alkyl; Linearity or branching, saturated or unsaturated C
1-C
6Single-or polyhydroxy alkyl; C
1-C
6Aminoalkyl group or polyalkyleneimine group.
For example, A can be a methylene radical, ethylidene, propylidene, methyl propylidene, ethyl propylidene, tetramethylene, pentamethylene, hexa-methylene, inferior dress base, phenyl two bases etc.
Ideally, A represents corresponding to one group in the following structural formula (a)-(d):
-CHR
1-CHR
2-CHR
3- (a)-CHR
′1-CHR
′2-CHR
′3-CHR
′4- (b)
-(CHR
1)
k-(CHR
2)-CH (CO
2H)-NH-(d) R wherein
1, R
2, R
3, R
' 1, R
' 2, R
' 3, R
' 4, R
1And R
2, can be identical or different, expression: hydrogen atom, linearity, branching or ring-type, saturated or undersaturated C
1-C
6Alkyl, amino-NH
2, carboxyl-COOH, C
1-C
10Alkylamino; R
" 1, R
" 2, R
" 3, R
" 4, can be identical or different, expression: hydrogen atom, linearity, or branching, saturated or undersaturated C
1-C
4Alkyl, arrow are illustrated in the position that replaces in the general formula (c), and k is an integer, preferred k=0 or 1.
Preferably, A is selected from:
-CH
2-CH (CO
2H)-NH-and Y=O
-(CH
2)
2-(CH
3CONH) CH-and Y=O
-(CH
2)
3-and Y=O or Y=NH.
Ideally, A is trimethylene-CH
2-CH
2-CH
2-, and Y=O, compound according to the present invention in this case are corresponding to following general formula (II):
Wherein: X represents nucleophilic group, and is preferred:
Sauerstoffatom
Or
Group-NR '-, wherein R ' is selected from hydrogen atom; Linearity or branching, saturated or unsaturated C
1-C
6Alkyl; Linearity or branching, saturated or unsaturated list-or polyhydroxy alkyl; C
1-C
6Aminoalkyl group or polyalkyleneimine group.
Preferably, according to the present invention, X is selected from: Sauerstoffatom and NH base.
For the situation of dendrimers, nucleophilic group X generally is a terminal functional groups.For highly-branched polymers such as polyethylene imine based, radicals X is in a branch of polymkeric substance rather than the secondary amine of seeing on the end position.
According to the present invention, more satisfactory is that the radicals X of at least 10% (by number) of highly-branched polymers or dendrimers is in order to functional group's grafting down:
HS-CH
2-CH
2-CH
2-CO-and even more preferably at least 40%.Can be by following group:
HS-CH
2-CH
2-CH
2In the highly-branched polymers or dendrimers that-CO-replaces, thiol functional group is with respect to the percentage ratio of the sum of the X of functional group, adapted to the further feature function of the character of the number in generation and trunk especially be adjusted into highly-branched polymers or dendrimers, and as the function of the solubleness of estimated performance especially highly-branched polymers or dendrimers.This accommodation can be undertaken by simple experiment by technician in the art.
Theme of the present invention also is the first method that preparation contains the highly-branched polymers or the dendrimers of thiol end group, the method is characterized in that, contain the starting polymer selected the highly-branched polymers of nucleophilic functional group and the dendrimers and thiolactone or imino-thia penta ring from end group or chain and react by following reaction formula:
Wherein
Expression contains dendrimers or the highly-branched polymers of the n XH of functional group as defined above, and m is that integer m≤n and A represent corresponding to one group in the following formula (a)-(d):
-CHR
1-CHR
2-CHR
3-(a)-CHR
' 1-CHR
' 2-CHR
' 3-CHR
' 4-(b)
-(CHR
1)
k-(CHR
2)-CH (CO
2H)-NH-(d) R wherein
1, R
2, R
3, R
' 1, R
' 2, R
' 3, R
' 4, R
1And R
2, can be identical or different, expression: hydrogen atom, linearity or branching, saturated or undersaturated C
1-C
6Alkyl, amino-NH
2, carboxyl-COOH, C
1-C
10Alkylamino; R
" 1, R
" 2, R
" 3And R
" 4, can be identical or different, expression: hydrogen atom, linearity or branching, saturated or unsaturated C
1-C
4Alkyl, arrow are illustrated in the position that replaces in the general formula (C); K is an integer, preferred k=0 or 1.
Preferably, in the method according to the invention, compound
Be selected from 2-oxo-4-thiazolidinecarboxylic acid, be also referred to as procysteine:
N-ethanoyl homocysteine thiolactone (N-acetyl homocysteinethiolactone):
γ-sulfo-butyrolactone
Imino-thia penta ring:
Ideally, in the method according to the invention, use to be selected from procysteine, the reactant of N-ethanoyl homocysteine thiolactone and γ-sulfo-butyrolactone.
Ideally, in the method according to the invention, compound
It is γ-sulfo-butyrolactone.
γ-sulfo-butyrolactone is the commercially available prod.
The reaction of opening thiolactone or imino-thia penta ring generally is at water or at aromatic solvent such as toluene or pure as methyl alcohol, ethanol, and in Virahol or the butanols, also (boiling point that depends on solvent) carries out under the temperature between 0-110 ℃ under inert atmosphere.
Yet, according to preferred form of the present invention, this reaction is to carry out in water, in this case, (with respect to the functional group of polymkeric substance-XH) mix, mixture is adjusted to 0-110 ℃ temperature to dendrimers or highly-branched polymers and thiolactone or imino-thia penta ring then under inert atmosphere in stoichiometric ratio.
When unhindered amina in n the functional group of needs preservation highly-branched polymers or dendrimers or hydroxy functional group, use thiolactone or imino-thia penta toroidal molecule/every dendrimers molecule or the every highly-branched polymers molecule of aequum m, in order that obtain to have the dendrimers or the highly-branched polymers of n-m unhindered amina or hydroxy functional group and m thiol functional group.
The alkalescence that depends on dendrimers or highly-branched polymers, the reaction times can be between 1-48 hour, and reaction process is monitored by the appearance of analysis thiol and/or the disappearance of amine functional group or alcohol functional group.Also might monitor the conversion of starting polymer by electrophoresis method.
Ideally, when group-A-contains free acid functional group or unhindered amina functional group, this functional group of neutralization before joining starting polymer in the reaction medium.
If a certain amount of thiol is oxidized to corresponding disulphide in reaction process, then reaction mixture is used the water dilution of its volume of twice and was stirred 1-3 hour in the presence of zinc powder in acidic medium.After most of disulphide were reduced, mixture filtered then, obtained the solution of required compound, and it can directly use.
The dendrimers and the highly-branched polymers that contain the mercaptoalkyl amide functional group also can be obtained by the sulfydryl paraffinic acid of correspondence or the amidate action of its ester in the known manner.This method can be represented by following reaction formula:
X wherein, n, m, A and
Have with above same meaning and Q and represent that hydrogen atom is saturated or undersaturated, C linear or branching
1-C
10Alkyl.
Yet above-described preparation method with the penta ring beginning of thiolactone or imino-thia is than comparatively fast and not causing forming by product, by product usually to have very odour nuisance and polluting final product.
Contain the highly-branched polymers of amine functional group and the following document of dendrimers referring to describing end group, the content of these documents is introduced in this specification sheets for reference: US-4 694 064, and US-4 507 466, US-4 631 337, and US-4 558 120, and US-4 568 737, US-4 587329, WO-A-9502008, WO-A-9314147, EP-234408, US-4 289 872, and US-4 360 646, proc.Natl.Acad.Sci.USA, 85,5409-5413 (1988); WO95/02008, WO93/14147; J.Am.Chem.Soc.117,9764 (1195); FR-2 734 268.
The dendrimers that contains the end group that carries primary amine functional group is the polyamide-based amine, as those (segmented copolymers of quadrol and methyl acrylate) of being sold with trade(brand)name Starburst PAMAN by Dendritech company.They also are selected from polyalkylene polyamine type dendrimers, as the polyethylene imine based and polytrimethylene imines made by DSM N. V. and be described in the following patent: WO93/14147 and WO95/02008.They also belong to polylysine family, described in US patent 4 360 646.In highly-branched polymers, can mention polyalkylene polyamine class such as polyethylene imine based, sell with trade mark Polymin and Lupasol by BASF AG.
The highly-branched polymers and the dendrimers that contain amine functional group also are made up of the core of any character and elementary cell, monomer or the trunk of Ge Dai, on them grafting carry the end group T of amine functional group.
The highly-branched polymers and the dendrimers (the especially polymkeric substance of polyester family) that contain hydroxyl end groups are described in the following document, and its content is introduced in this specification sheets for reference: US4 587329; WO93/17060; WO92/14543; J.Am.Chem.Soc., 113,4583-4588 (1991); Macromolecules 25,4583-4587 (1992); US5 196 502; US 5 214 122.
Preferably, starting polymer is selected from dendrimers.
After reaction, the core of starting polymer and ramose character do not change.Also possible, as the function of the ratio of use reactant, some initial end groups do not have modification.Therefore, if begin with polyamide-based amine (handling with γ-sulfo-butyrolactone), method of the present invention will obtain containing the polymeric amide of sulfydryl-4-butyramide terminal functional groups.Begin with polyalkylene polyamine, method of the present invention obtains with sulfydryl-4-butyramide functional group grafted polyalkylene polyamine.Begin with polyester, method of the present invention will obtain containing the polyester of sulfydryl-4-butyramide terminal functional groups.
These new polymerss have reducing property and replace reductive agent commonly used, are used for for example makeup, as nursing nail and hair.Especially, these new polymerss can be used as reductive agent in permanent wave shape wave Hairstyling composition.
Because polymkeric substance according to the present invention contains-the SH terminal functional groups, they can protect the product responsive especially to oxidation as protective agent.They can be used for the composition of any character as antioxidant, especially in makeup or pharmaceutical composition, for example in the shampoo of hair composition such as Hair grooming, lotion, gel, emulsion or hair jelly, rinse composition, these all are before or after hair washing for the fronts, before or after dyeing or bleaching, the permanent waveization of hair or stretching, in design with before handling lotion or gel, use in the process or afterwards; Dry up or the lotion of shaping hair or gel in and in the permanent waveization of hair, stretching, dyeing or bleaching composition, use.They can also be used for skin-protection product or cosmetic product as antioxidant, as the product of make-up eyelash, eyebrow or skin, as epidermis nursing creme, foundation cream, lipstick, eye shadow cream, kermes, Mascara, eyeliner or nail varnish, or be used for skin care or skin cleaning lotion, creme and cleansing milk.
Theme of the present invention also has a kind of composition, it makeup can with or dermatology in the acceptable carrier, comprise at least a polymkeric substance of the present invention.
In the time of in joining carrier, polymkeric substance of the present invention can form film because of the formation of intramolecular disulfide bridged bond, is therefore contained-dendrimers of SH terminal functional groups or the polymkeric substance of highly-branched polymers.
This film can form from several thiol functional group, and other functional group keeps free and can have reductive action.
Polymkeric substance of the present invention can be expected directly being used in as the use of antioxidant in the solution in the medium of being afraid of oxidation, and this is for standard anti-oxidant such as Thiovanic acid, and thiolactic acid or halfcystine are common.
If polymkeric substance is insoluble in the medium of being afraid of oxidation, also might expect it for example is fixed in the inwall or stopper of the bottle that protected prescription is housed with film or pellet form.
Under second kind of situation, dendrimers of the present invention or highly-branched polymers also can be with a spot of usually as a kind of combination the in those thiols of antioxidant, for example Thiovanic acid, thiolactic acid or halfcystines.This might limit the amount of solubility thiol in the protected composition and therefore limit the drawbacks common-smell relevant with it in conjunction with feasible, the change color-and keep its remarkable effectiveness simultaneously.Therefore theme of the present invention also is this combination.
Especially have such advantage according to highly-branched polymers of the present invention and dendrimers: its smell than usually as the thiol of antioxidant weak many-their odorlessnesses in fact at room temperature.
Because their ad hoc structure is penetrated in the keratin layer or in epidermis hardly according to highly-branched polymers of the present invention and dendrimers, they therefore be non-sensibility and do not have a toxicity problem.
Providing limiting examples below describes.
Embodiment
Embodiment 1: have 8 surperficial SH functional groups, the 1st generation contain quadrol core, the dendrimers of quadrol and methyl acrylate trunk
In inert atmosphere at room temperature, γ-sulfo-butyrolactone of 540 μ l (i.e. 1 equivalent that calculates with respect to all primary amine functional groups) is joined 2g to be contained in the aqueous solution of dendrimers of 55.7g/100g, this dendrimers is sold with trade(brand)name PAMANStarburst by Dendritech company and is had a quadrol core, belong to the 1st generation (8 amido functional groups), with the dilution of 2ml water.Be initially heterogeneous medium and become homogeneous phase (1 hour) fast.After stirring 48 hours, only in medium, find the γ-sulfo-butyrolactone of trace.Mixture is with 10ml ether washing 3 times, with the water of nitrogen bubble by so obtaining, to remove the ether of any trace.
So the aqueous solution that obtains is analyzed by NMR.Recording all initial primary amine functional groups all gets-NH-CO-(CH
2)
3-SH form.
The activity substance content of this water is 37.71g/100g.So but the dendrimers former state that obtains just can be used in the aqueous solution.The molar mass of institute's synthetic product: 2247gmol
-1
Empirical formula: C
94H
176N
26O
20S
8
Embodiment 2:
Have 16 surperficial NH
2In the 3rd generation of the surperficial SH of functional group and 16 functional group, have the dendrimers of quadrol core, quadrol and methyl acrylate trunk
In inert atmosphere at room temperature, γ-sulfo-butyrolactone of 384 μ l (i.e. 0.5 equivalent that calculates with respect to all primary amine functional groups) is joined 4g to be contained in the aqueous solution of dendrimers of 47.85g/100g, this dendrimers is sold with trade(brand)name PAMANStarburst by Dendritech company and is had a quadrol core, belong to the 3rd generation (32 surface amino groups functional groups), with the dilution of 4ml water.After interpolation, heterogeneous medium becomes homogeneous phase (1 hour) fast.After stirring 20 hours, in medium, do not detect γ-sulfo-butyrolactone.
So the aqueous solution that obtains is analyzed by NMR.Recording 50% initial primary amine functional group gets-NH-CO-(CH
2)
3-SH form.
The activity substance content of this water is 27.75g/100g.So the dendrimers former state that obtains just can be used in the aqueous solution.The molar mass of institute's synthetic product: 8532gmol
-1
Empirical formula: C
366H
704N
122O
76S
16
Embodiment 3:
Have 1.6 surperficial NH
2In the 1st generation of the surperficial SH of functional group and 6.4 functional group, have the dendrimers of quadrol core, quadrol and methyl acrylate trunk
In inert atmosphere at room temperature, γ-sulfo-butyrolactone of 431 μ l (i.e. 0.8 equivalent that calculates with respect to all primary amine functional groups) is joined 2g to be contained in the aqueous solution of dendrimers of 55.7g/100g, this dendrimers is sold with trade(brand)name PAMANStarburst by Dendritech company and is had the quadrol core, belongs to the 1st generation (8 surperficial NH
2Functional group), with the dilution of 2ml water.Be initially heterogeneous medium and become homogeneous phase (1 hour) fast.After stirring 24 hours, in medium, do not detect γ-sulfo-butyrolactone.
So the aqueous solution that obtains is analyzed by NMR.Recording 80% initial primary amine functional group gets-NH-CO-(CH
2)
3-SH form.
The activity substance content of this water is 35.99g/100g.So the dendrimers former state that obtains just can be used in the aqueous solution.The molar mass of institute's synthetic product: 2080.8gmol
-1Empirical formula: C
87.6H
166.4N
26O
18.4S
6.4
Embodiment 4: the polyethylene imine based polymkeric substance of branching with average molecular weight Mw=1200 of 6.75 SH functional groups
In the polyethylene imine based 3g of the being diluted in water of average molecular weight Mw=1200 that 1g is sold by Polysciences company and the γ-sulfo-butyrolactone (i.e. 6.75 molar equivalents that calculate with respect to the molecular-weight average of polymkeric substance) of in inert atmosphere, at room temperature adding 482 μ l.Be initially heterogeneous medium and become homogeneous phase (about 30 minutes) fast.After stirring 2 hours, in medium, do not detect γ-sulfo-butyrolactone.In the sure reaction of sodium nitroprusside development (developing) water generation afterwards.Therefore can observe some initial primary amine functional groups gets NH-CO-(CH
2)
3-SH form.
The activity substance content of this water is 34.35g/100g.So the dendrimers former state that obtains just can be used in the aqueous solution.The molar mass of institute's synthetic product: 1889.6gmol
-1
Claims (23)
1, be selected from the polymkeric substance of highly-branched polymers and dendrimers, it is characterized in that they contain functional group corresponding to general formula (I):
Wherein: Y represents Sauerstoffatom or NH group,
A represents linearity, branching or ring-type, saturated or unsaturated C
1-C
12Alkane 2 basis; This alkane 2 basis arbitrariness ground inserts one or more heteroatomss, as O or N;
This alkane 2 basis can be replaced by a following functional group to arbitrariness:
-amino :-NH
2, be to arbitrariness form inorganic or organic acid salt,
-amido :-NH-COR, wherein R represents linearity, branching or ring-type, saturated or unsaturated C
1-C
10Alkyl,
-carboxylic acid,
-C
1-C
10Ester;
X represents nucleophilic group.
2,, it is characterized in that A represents corresponding to one group in the following structural formula (a)-(d) according to the polymkeric substance of claim 1:
-CHR
1-CHR
2-CHR
3- (a)
-CHR
' 1-CHR
' 2-CHR
' 3-CHR
' 4-(b)
-(CHR
1)
k-(CHR
2)-CH (CO
2H)-NH-(d) R wherein
1, R
2, R
3, R
' 1, R
' 2, R
' 3, R
' 4, R
1And R
2, can be identical or different, expression: hydrogen atom, linearity, branching or ring-type, saturated or undersaturated C
1-C
6Alkyl, amino-NH
2, carboxyl-COOH, C
1-C
10Alkylamino; R
" 1, R
" 2, R
" 3, R
" 4, can be identical or different, expression: hydrogen atom, linearity or branching, saturated or undersaturated C
1-C
4Alkyl, arrow are illustrated in the position that replaces in the general formula (c), and k is an integer, preferred k=0 or 1.
3, according to the polymkeric substance of aforementioned claim, it is characterized in that:
A=-CH
2-CH (CO
2H)-NH-and Y=O
Or
A=-(CH
2)
2-(CH
3CONH) CH-and Y=O
Or
A=-(CH
2)
3-and Y=O
Or A=-(CH
2)
3-and Y=NH.
4,, it is characterized in that A is a trimethylene :-CH according to the polymkeric substance of aforementioned claim
2-CH
2-CH
2-, and Y=O.
5, according to any one polymkeric substance in the aforementioned claim, it is characterized in that X represents:
Sauerstoffatom
Or
Group-NR '-, wherein R ' is selected from hydrogen atom; Linearity or branching, saturated or unsaturated C
1-C
6Alkyl; Linearity or branching, saturated or unsaturated C
1-C
6Single-or polyhydroxy alkyl; C
1-C
6Aminoalkyl group or polyalkyleneimine group.
6,, it is characterized in that X is selected from Sauerstoffatom and NH group according to the polymkeric substance of claim 5.
7, according to any one polymkeric substance among the claim 1-6, the radicals X that it is characterized in that at least 10% (by number) of highly-branched polymers or dendrimers is in order to functional group's grafting down:
HS-CH
2-CH
2-CH
2-CO-
With in addition more preferably at least 40%.
8, according to any one polymkeric substance in the aforementioned claim, it is characterized in that it belongs to polymeric amide family.
9, according to any one polymkeric substance among the claim 1-7, it is characterized in that it belongs to polyalkylene polyamine family.
10,, it is characterized in that it is polyethylene imine based according to the polymkeric substance of claim 9.
11, according to any one polymkeric substance among the claim 1-7, it is characterized in that it belongs to polyester family.
12, according to any one polymkeric substance in the aforementioned claim, it is characterized in that it belongs to dendrimers family.
13, the method for the polymkeric substance of any one among the preparation claim 1-12 is characterized in that: contain the starting polymer of selecting the highly-branched polymers of nucleophilic functional group and the dendrimers from end group or chain and encircle with thiolactone or imino-thia penta and react by following reaction formula:
Wherein
Expression contains dendrimers or the highly-branched polymers of n terminal functional groups XH, and X represents nucleophilic group, and m is that integer m≤n and A represent corresponding to one group in the following formula (a)-(d):
-CHR
1-CHR
2-CHR
3- (a)
-CHR
' 1-CHR
' 2-CHR
' 3-CHR
' 4-(b)
-(CHR
1)
k-(CHR
2)-CH (CO
2H)-NH-(d) R wherein
1, R
2, R
3, R
' 1, R
' 2, R
' 3, R
' 4, R
1And R
2, can be identical or different, expression: hydrogen atom, linearity or branching, saturated or undersaturated C
1-C
6Alkyl, amino-NH
2, carboxyl-COOH, C
1-C
10Alkylamino; R
" 1, R
" 2, R
" 3And R
" 4, can be identical or different, expression: hydrogen atom, linearity or branching, saturated or unsaturated C
1-C
4Alkyl, arrow are illustrated in the position that replaces in the general formula (C); K is an integer, preferred k=0 or 1.
14, according to the method for last claim, it is characterized in that:
Be selected from
Procysteine:
N-ethanoyl homocysteine thiolactone:
γ-sulfo-butyrolactone:
Imino-thia penta ring:
15, according to the method for aforementioned claim, it is characterized in that:
It is γ-sulfo-butyrolactone.
16, according to any one method among the claim 13-15, it is characterized in that: the reaction of opening thiolactone or imino-thia penta ring is in aromatic solvent or alcohol, carries out under inert atmosphere and under the temperature between 0-110 ℃.
17, according to any one method among the claim 13-15, it is characterized in that: this reaction is to carry out in water, carry out in the presence of by the starting polymer of stoichiometric ratio and thiolactone or imino-thia penta ring, mixture is adjusted to 0-110 ℃ temperature then under inert atmosphere.
18, preparation is characterised in that according to the method for the polymkeric substance of any one among the claim 1-12: contain the highly-branched polymers of nucleophilic functional group and starting polymer that dendrimers is selected and sulfydryl paraffinic acid or sulfydryl alkanoates and react according to following reaction formula from end group or chain:
N wherein, m and
Have with claim 13 in same meaning, A and X have with claim 1 in same meaning and Q represent that hydrogen atom is saturated or undersaturated, C linear or branching
1-C
10Alkyl.
19, according to the purposes of the polymkeric substance of any one among the claim 1-12, be used as reductive agent.
20, according to the purposes of the polymkeric substance of any one among the claim 1-12, be used as antioxidant.
21, a kind of composition is characterized in that: comprise: makeup can with or dermatology in the acceptable carrier, have at least a according to any one polymkeric substance among the claim 1-12.
22, at least a according to any one polymkeric substance and selected from mercapto acetate among the claim 1-12, the binding substances of at least a compound of thiolactic acid or halfcystine.
23, make-up composition is characterized in that: it comprises: in the makeup available support, and the binding substances of with good grounds claim 22.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9704085A FR2761691B1 (en) | 1997-04-03 | 1997-04-03 | THIOL TERMINAL FUNCTION POLYMERS |
| FR97/04085 | 1997-04-03 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1259152A true CN1259152A (en) | 2000-07-05 |
Family
ID=9505489
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98805803A Pending CN1259152A (en) | 1997-04-03 | 1998-03-26 | Polymers with thiol terminal function |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US6395867B1 (en) |
| EP (1) | EP0971972B1 (en) |
| JP (1) | JP3413212B2 (en) |
| CN (1) | CN1259152A (en) |
| AT (1) | ATE264357T1 (en) |
| AU (1) | AU7052298A (en) |
| BR (1) | BR9815464A (en) |
| CA (1) | CA2284896A1 (en) |
| DE (1) | DE69823177T2 (en) |
| ES (1) | ES2219884T3 (en) |
| FR (1) | FR2761691B1 (en) |
| HU (1) | HUP0002321A2 (en) |
| MX (1) | MX9908947A (en) |
| PL (1) | PL336002A1 (en) |
| WO (1) | WO1998044024A1 (en) |
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| CN102307851A (en) * | 2008-12-11 | 2012-01-04 | 3M创新有限公司 | Amide-linked perfluoropolyether thiol compounds and processes for their preparation and use |
| CN101402738B (en) * | 2007-07-23 | 2012-06-06 | 中国科学院成都有机化学有限公司 | Cationic polymer |
| CN112724403A (en) * | 2019-10-14 | 2021-04-30 | 中国科学院上海有机化学研究所 | Poly (gamma-thiobutyrolactone) and preparation method thereof |
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| FR2772771B1 (en) * | 1997-12-19 | 2000-01-28 | Oreal | USE OF HYPERBRANCHED POLYMERS AND DENDRIMERS HAVING A PARTICULAR GROUPING, AS A FILM-FORMING AGENT, FILM-FORMING COMPOSITIONS COMPRISING THEM AND THEIR USE IN PARTICULAR IN COSMETICS OR PHARMACY |
| FR2772770B1 (en) | 1997-12-19 | 2000-01-28 | Oreal | NOVEL COMPOUNDS SELECTED AMONG HYPERBRANCHED POLYMERS AND DENDRIMERS HAVING A PARTICULAR GROUPING, METHOD OF PREPARATION, USE AND COMPOSITIONS COMPRISING THE SAME |
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| NO322724B1 (en) | 2004-04-15 | 2006-12-04 | Sinvent As | Process for preparing polybranched organic / inorganic hybrid polymer |
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-
1997
- 1997-04-03 FR FR9704085A patent/FR2761691B1/en not_active Expired - Fee Related
-
1998
- 1998-03-26 JP JP54123498A patent/JP3413212B2/en not_active Expired - Fee Related
- 1998-03-26 BR BR9815464-8A patent/BR9815464A/en not_active IP Right Cessation
- 1998-03-26 WO PCT/FR1998/000620 patent/WO1998044024A1/en active IP Right Grant
- 1998-03-26 DE DE69823177T patent/DE69823177T2/en not_active Expired - Fee Related
- 1998-03-26 AU AU70522/98A patent/AU7052298A/en not_active Abandoned
- 1998-03-26 AT AT98917248T patent/ATE264357T1/en not_active IP Right Cessation
- 1998-03-26 MX MX9908947A patent/MX9908947A/en unknown
- 1998-03-26 ES ES98917248T patent/ES2219884T3/en not_active Expired - Lifetime
- 1998-03-26 EP EP98917248A patent/EP0971972B1/en not_active Expired - Lifetime
- 1998-03-26 PL PL98336002A patent/PL336002A1/en unknown
- 1998-03-26 US US09/402,201 patent/US6395867B1/en not_active Expired - Fee Related
- 1998-03-26 HU HU0002321A patent/HUP0002321A2/en unknown
- 1998-03-26 CN CN98805803A patent/CN1259152A/en active Pending
- 1998-03-26 CA CA002284896A patent/CA2284896A1/en not_active Abandoned
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1957010B (en) * | 2004-04-30 | 2010-06-16 | 佳能精技股份有限公司 | Antioxidants and recording media made by using the same |
| CN101402738B (en) * | 2007-07-23 | 2012-06-06 | 中国科学院成都有机化学有限公司 | Cationic polymer |
| CN102307851A (en) * | 2008-12-11 | 2012-01-04 | 3M创新有限公司 | Amide-linked perfluoropolyether thiol compounds and processes for their preparation and use |
| CN112724403A (en) * | 2019-10-14 | 2021-04-30 | 中国科学院上海有机化学研究所 | Poly (gamma-thiobutyrolactone) and preparation method thereof |
| CN112724403B (en) * | 2019-10-14 | 2022-10-04 | 中国科学院上海有机化学研究所 | Poly (gamma-thiobutyrolactone) and preparation method thereof |
| CN114765982A (en) * | 2020-11-13 | 2022-07-19 | 三井化学株式会社 | Polythiol composition, polymerizable composition, resin, molded body, optical material, and lens |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0971972A1 (en) | 2000-01-19 |
| MX9908947A (en) | 2000-01-31 |
| DE69823177D1 (en) | 2004-05-19 |
| JP2000509763A (en) | 2000-08-02 |
| FR2761691B1 (en) | 1999-05-14 |
| ES2219884T3 (en) | 2004-12-01 |
| US6395867B1 (en) | 2002-05-28 |
| JP3413212B2 (en) | 2003-06-03 |
| FR2761691A1 (en) | 1998-10-09 |
| PL336002A1 (en) | 2000-06-05 |
| ATE264357T1 (en) | 2004-04-15 |
| DE69823177T2 (en) | 2005-04-14 |
| BR9815464A (en) | 2001-07-31 |
| EP0971972B1 (en) | 2004-04-14 |
| AU7052298A (en) | 1998-10-22 |
| CA2284896A1 (en) | 1998-10-08 |
| WO1998044024A1 (en) | 1998-10-08 |
| HUP0002321A2 (en) | 2000-11-28 |
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